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Feature Article
Chem. Commun., 2009, 4781 - 4790, DOI: 10.1039/b907036b
Ligand-enabled PtII–C(sp3) bond functionalization with dioxygen as a direct oxidant
Andrei N. Vedernikov
This feature article summarizes the progress achieved in the field of aerobic functionalization of PtII monoalkyl complexes in protic solvents, water and alcohols. These functionalization reactions are possible in the presence of tripodal semi-labile ligands such as di(2-pyridyl)methanesulfonate (dpms). The reactions include two subsequent transformations: (i) direct (mediatorless) oxidation of a PtII monoalkyl or a PtII-oxetane to produce a PtIV(OH) alkyl or a PtIV(OH)-oxetane, respectively, and (ii) reductive elimination from the PtIV center of an oxygenated organic derivative with a new C–O bond such as alcohols (MeOH, HOC2H4OH), ethers (Me2O), or olefin (ethylene, cis-cyclooctene, norbornene) oxides. All the reactions are highly chemo- and stereoselective. Mechanisms of dioxygen activation with (dpms)PtII alkyls and C–O reductive eliminations from a PtIV center are discussed, including the direct C–O elimination of epoxides from PtIV oxetanes previously undocumented for this metal. Modification of the
slow
PtII-based systems led to the discovery of a fast dioxygenase-like acetoxylation of benzylic C–H bonds catalyzed by homogeneous Pd complexes with O2 as the sole oxidant.
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